Herbicidal N-[(4-bromo-6-methoxypyrimidin-2-yl)aminocarbonyl]-2,3-dihydro-(2-methyl)benzo[b]thiophene-7-sulfonamides, 1,1-dioxide

ABSTRACT

Benzofuran and benzothiophene sulfonamides show utility as herbicides and plant growth regulants.

BACKGROUND OF THE INVENTION

This invention relates to benzofuran and benzothiophene sulfonamides which are novel. The compounds of this invention and their agriculturally suitable salts, are useful as agricultural chemicals, e.g., plant growth regulants and herbicides.

Netherlands Pat. No. 121,788, published Sept. 15, 1966, discloses the preparation of compounds of the following Formula and their use as general or selective herbicides: ##STR1## wherein R₁ and R₂ may independently be alkyl of 1-4 carbon atoms; and

R₃ and R₄ may independently be hydrogen, chlorine or alkyl of 1-4 carbon atoms.

U.S. Pat. No. 3,637,366 discloses compounds having the formula: ##STR2## wherein R₁ is hydrogen or lower saturated aliphatic acyl and

R₂ is hydrogen, 2-pyrimidinyl, pyridyl, amidino, acetyl or carbamoyl.

The disclosed compounds are said to provide control of crabgrass, cress, endive, clover and Poa annua.

French Pat. No. 1,468,747 discloses the following para-substituted phenylsulfonamides as being useful as antidiabetic agents: ##STR3## wherein R=H, halogen, CF₃ or alkyl.

Logemann et al., Chem. Ab., 53, 18052 g (1959), disclose a number of sulfonamides, including uracil derivatives and those having the formula: ##STR4## wherein R is butyl, phenyl or ##STR5## and R₁ is hydrogen or methyl.

When tested for hypoglycemic effect in rats (oral doses of 25 mg/100 g), the compounds in which R is butyl and phenyl were most potent. The others were of low potency or inactive.

Wojciechowski, J. Acta. Polon. Pharm. 19, p. 121-5 (1962) [Chem. Ab., 59 1633 e] describes the synthesis of N-[(2,6-dimethoxypyrimidin-4-yl)aminocarbonyl]-4-methylbenzenesulfonamide: ##STR6##

U.S. Pat. No. 4,127,405 teaches compounds which are useful for controlling weeds in wheat having the formula ##STR7## wherein R is ##STR8## R₁ is ##STR9## R₃ and R₆ are independently hydrogen, fluorine, chlorine, bromine, iodine, alkyl of 1-4 carbon atoms, alkoxy of 1-4 carbon atoms, nitro, trifluoromethyl, cyano, CH₃ S(O)_(n) -- or CH₃ CH₂ S(O)_(n) ;

R₄ is hydrogen, fluorine, chlorine, bromine or methyl;

R₅ is hydrogen, fluorine, chlorine, bromine, methyl or methoxy;

R₇ is hydrogen, fluorine, chlorine, bromine, alkyl of 1-2 carbon atoms or alkoxy of 1-2 carbon atom;

R₈ is hydrogen, methyl, chlorine or bromine;

R₉ and R₁₀ are independently hydrogen, methyl, chlorine or bromine;

W and Q are independently oxygen or sulfur;

n is 0, 1 or 2;

X is hydrogen, chlorine, bromine, methyl, ethyl, alkoxy of 1-3 carbon atoms, trifluoromethyl, CH₃ S-- or CH₃ OCH₂ --; and

Z is methyl or methoxy;

or their agriculturally suitable salts; provided that:

(a) when R₅ is other than hydrogen, at least one of R₃, R₄, R₆ and R₇ is other than hydrogen and at least two of R₃, R₄, R₆ and R₇ must be hydrogen;

(b) when R₅ is hydrogen and all of R₃, R₄, R₆ and R₇ are other than hydrogen, then all of R₃, R₄, R₆ and R₇ must be either chlorine or methyl; and

(c) when R₃ and R₇ are both hydrogen, at least one of R₄, R₅ or R₆ must be hydrogen.

The presence of undesired vegetation causes substantial damage to useful crops, especially agricultural products that satisfy man's basic food and fiber needs, such as cotton, rice, corn, wheat, and the like. The current population explosion and concomitant world food and fiber shortage demand improvements in the efficiency of producing these crops. Prevention or minimizing the loss of a portion of such valuable crops by killing, or inhibiting the growth of undesired vegetation is one way of improving this efficiency. A wide variety of materials useful for killing, or inhibiting (controlling) the growth of undesired vegetation is available; such materials are commonly referred to as herbicides. The need still exists however, for more effective, selective herbicides.

SUMMARY OF THE INVENTION

This invention relates to novel compounds of Formula I, agriculturally suitable compositions containing them and their method-of-use as selective preemergent or postemergent herbicides. ##STR10## wherein J is ##STR11## n is 1 or 2; Q is O, S, SO or SO₂ ;

R₁ is H, Cl, CH₃ or OCH₃ ;

R₂ is H or C₁ -C₄ alkyl;

R₃ is H or CH₃ ;

R₄ is H or CH₃ ;

provided that when R₃ is CH₃, then Q is SO₂ and R₂ is CH₃ ; and their agriculturally suitable salts.

Specifically preferred are:

N-[(4-bromo-6-methoxypyrimidin-2-yl)aminocarbonyl]-2,3-dihydrobenzo[b]thiophene-7-sulfonamide, 1,1-dioxide, m.p. 238°-240° C.; and

N-[(4-bromo-6-methoxypyrimidin-2-yl)aminocarbonyl]-2,3-dihydro-2-methylbenzo[b]thiophene-7-sulfonamide, 1,1dioxide, m.p. 225°-227° C.

DETAILED DESCRIPTION OF THE INVENTION Synthesis

The compounds of Formula I where Q is other than SO can be prepared by reacting the appropriate sulfonyl isocyanate of Formula II with 2-amino-4-bromo-6-methoxypyrimidine III as shown in Equation 1. ##STR12##

The reaction is carried out at 25° to 100° C. in an inert, aprotic solvent such as methylene chloride or xylene for 0.5 to 24 hours as taught in U.S. Pat. No. 4,127,405.

Alternatively, compounds of Formula I can be prepared by reacting a sulfonyl carbamate of Formula IV with amine III as shown in Equation 2. ##STR13##

The reaction is carried out at 50° to 100° C. in a solvent such as dioxane for 0.5 to 24 hours as taught in EPO Publication No. 44,807. The required carbamates IV are prepared by reacting the corresponding sulfonamides V with diphenylcarbonate or phenylchloroformate in the presence of base.

The compounds of Formula I can also be prepared by reacting a sulfonamide of Formula V with O-phenyl-N-(4-bromo-6-methoxypyrimidin-2-yl)carbamate VI in the presence of base as shown in Equation 3. ##STR14##

The reaction is carried out at 0° to 50° C. in an inert solvent such as acetonitrile for 0.1 to 24 hours in the presence of a base such as 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) as taught in EPO Publication No. 44,807. The required carbamate VI is prepared by reacting amine III with diphenylcarbonate or phenylchloroformate in the presence of base.

Compounds of Formula I where Q is SO can be prepared via oxidation of the corresponding compounds of Formula I where Q is S by standard methods known to one skilled in the art.

The intermediate sulfonyl isocyanates of Formula II and sulfonamides of Formula V can be prepared by methods which would be obvious to one skilled in the art such as those taught in EPO Publication No. 79,683 and in South African Patent Application No. 83/5165.

2-Amino-4-bromo-6-methoxypyrimidine III is known, see T. Hirayama, et. al. Heterocycles, 2, 461 (1974) and Chem. Pharm. Bull. 24, 507 (1976). It can also be prepared by contacting 2-amino-4,6-dibromopyrimidine with one equivalent of sodium methoxide in methanol.

Agriculturally suitable salts of compounds of Formula I are also useful herbicides and can be prepared in a number of ways known to the art. For example, metal salts can be made by contacting compounds of Formula I with a solution of an alkali or alkaline earth metal salt having a sufficiently basic anion (e.g., hydroxide, alkoxide, carbonate or hydroxide). Quaternary amine salts can be made by similar techniques.

Salts of compounds of Formula I can also be prepared by exchange of one cation for another. Cationic exchange can be effected by direct contact of an aqueous solution of a salt of a compound of Formula I (e.g., alkali or quaternary amine salt) with a solution containing the cation to be exchanged. This method is most effective when the desired salt containing the exchanged cation is insoluble in water and can be separated by filtration.

Exchange may also be effected by passing an aqueous solution of a salt of a compound of Formula I (e.g., an alkali metal or quaternary amine salt) through a column packed with a cation exchange resin containing the cation to be exchanged for that of the original salt and the desired product is eluted from the column. This method is particularly useful when the desired salt is water-soluble.

Acid addition salts, useful in this invention, can be obtained by reacting a compound of Formula I with a suitable acid, e.g., p-toluenesulfonic acid, trichloroacetic acid or the like.

The following example teaches the synthesis of a compound of this invention in greater detail.

EXAMPLE 1 N-[(4-Bromo-6-methoxypyrimidin-2-yl)aminocarbonyl]-2,3-dihydrobenzo[b]thiophene-7-sulfonamide, 1,1-dioxide

A suspension of 5.0 g (20 mmol) of 2,3-dihydrobenzo[b]thiophene-7-sulfonamide-1,1-dioxide in 50 mL of thionyl chloride was refluxed for 40 hours, cooled, diluted with 100 mL of dry toluene and fractionally distilled to remove excess thionyl chloride. The cooled toluene solution was contacted with 2 drops of pyridine and 3 mL of liquified phosgene and the mixture was refluxed for 3 hours, cooled and concentrated in vacuo to give 5.8 g of 2,3-dihydrobenzo[b]thiophene-7-sulfonylisocyanate-1,1-dioxide as a brown powder whose IR spectrum exhibited a strong band at 2250 cm⁻¹.

A solution of 1.4 g (5 mmol) of the crude isocyanate and 0.82 g (4 mmol) of 2-amino-4-bromo-6-methoxypyrimidine in 20 mL of dry methylene chloride was heated to reflux for 5 minutes and stirred at room temperature for 16 hours. The resulting precipitate was filtered, washed with dry methylene chloride and anhydrous ether and air dried to give 1.6 g of the title compound as a white powder, m.p. 238°-240° C.

200 MHz ¹ H NMR (DMSO-d₆): δ 12.2 (br, 1H, NH); 10.9 (b, 1H, NH); 8.1 (m, 1H, arom); 7.9 (m, 2H, arom); 7.0 (s, 1H, CH) 4.0 (s, 3H, OCH₃); 3.7 (m, 2H, CH₂); and 3.4 (m, 2H, CH₂) ppm.

IR (nujol): 3380, 1730, 1710 cm⁻¹.

The following compounds can be prepared by one skilled in the art using the proper reactants and the procedures outlined above.

                  TABLE I                                                          ______________________________________                                          ##STR15##                                                                     n   Q      R.sub.1   R.sub.2     R.sub.3                                                                              m.p. (°C.)                       ______________________________________                                         1   O      H         H           H     197-201                                 1   O      H         CH.sub.3    H                                             1   O      H         CH.sub.2 CH.sub.3                                                                          H                                             1   O      H         CH.sub.2 CH.sub.2 CH.sub.3                                                                 H                                             1   O      H         CH.sub.2 CH.sub.2 CH.sub.2 CH.sub.3                                                        H                                             1   O      H         CH(CH.sub.3).sub.2                                                                         H                                             1   O      H         CH(CH.sub.3)CH.sub.2 CH.sub.3                                                              H                                             1   O      H         CH.sub.2 CH(CH.sub.3).sub.2                                                                H                                             1   O        -o-Cl   H           H                                             1   O        -o-Cl   CH.sub.3    H                                             1   O        -o-Cl   CH.sub.2 CH.sub.3                                                                          H                                             1   O        -o-Cl   CH.sub.2 CH.sub.2 CH.sub.3                                                                 H                                             1   O        -o-Cl   CH.sub.2 CH.sub.2 CH.sub.2 CH.sub.3                                                        H                                             1   O        -o-Cl   CH(CH.sub.3).sub.2                                                                         H                                             1   O        -o-Cl   CH(CH.sub.3)CH.sub.2 CH.sub.3                                                              H                                             1   O        -o-Cl   CH.sub.2 CH(CH.sub.3).sub.2                                                                H                                             1   O       .sub.--m-Cl                                                                             H           H                                             1   O       .sub.--m-Cl                                                                             CH.sub.3    H     208-211                                 1   O       .sub.--m-Cl                                                                             CH.sub.2 CH.sub.3                                                                          H                                             1   O       .sub.--m-Cl                                                                             CH.sub.2 CH.sub.2 CH.sub.3                                                                 H                                             1   O       .sub.--m-Cl                                                                             CH.sub.2 CH.sub.2 CH.sub.2 CH.sub.3                                                        H                                             1   O       .sub.--m-Cl                                                                             CH(CH.sub.3).sub.2                                                                         H                                             1   O       .sub.--m-Cl                                                                             CH(CH.sub.3)CH.sub.2 CH.sub.3                                                              H                                             1   O        .sub.--m-Cl                                                                            CH.sub.2 CH(CH.sub.3).sub.2                                                                H                                             1   O        -o-CH.sub.3                                                                            H           H                                             1   O        -o-CH.sub.3                                                                            CH.sub.3    H                                             1   O        -o-CH.sub.3                                                                            CH.sub.2 CH.sub.3                                                                          H                                             1   O        -o-CH.sub.3                                                                            CH.sub.2 CH.sub.2 CH.sub.3                                                                 H                                             1   O        -o-CH.sub.3                                                                            CH.sub.2 CH.sub.2 CH.sub.2 CH.sub.3                                                        H                                             1   O        -o-CH.sub.3                                                                            CH(CH.sub.3).sub.2                                                                         H                                             1   O        -o-CH.sub.3                                                                            CH(CH.sub.3)CH.sub.2 CH.sub.3                                                              H                                             1   O        -o-CH.sub.3                                                                            CH.sub.2 CH(CH.sub.3).sub.2                                                                H                                             1   O       .sub.--m-CH.sub.3                                                                       H           H                                             1   O       .sub.--m-CH.sub.3                                                                       CH.sub.3    H                                             1   O       .sub.--m-CH.sub.3                                                                       CH.sub.2 CH.sub.3                                                                          H                                             1   O       .sub.--m-CH.sub.3                                                                       CH.sub.2 CH.sub.2 CH.sub.3                                                                 H                                             1   O       .sub.--m-CH.sub.3                                                                       CH.sub.2 CH.sub.2 CH.sub.2 CH.sub.3                                                        H                                             1   O       .sub.--m-CH.sub.3                                                                       CH(CH.sub.3).sub.2                                                                         H                                             1   O       .sub.--m-CH.sub.3                                                                       CH(CH.sub.3)CH.sub.2 CH.sub.3                                                              H                                             1   O       .sub.--m-CH.sub.3                                                                       CH.sub.2 CH(CH.sub.3).sub.2                                                                H                                             1   O        -o-OCH.sub.3                                                                           H           H                                             1   O        -o-OCH.sub.3                                                                           CH.sub.3    H                                             1   O        -o-OCH.sub.3                                                                           CH.sub.2 CH.sub.3                                                                          H                                             1   O        -o-OCH.sub.3                                                                           CH.sub.2 CH.sub.2 CH.sub.3                                                                 H                                             1   O        -o-OCH.sub.3                                                                           CH.sub.2 CH.sub.2 CH.sub.2 CH.sub.3                                                        H                                             1   O        -o-OCH.sub.3                                                                           CH(CH.sub.3).sub.2                                                                         H                                             1   O        -o-OCH.sub.3                                                                           CH(CH.sub.3)CH.sub.2 CH.sub.3                                                              H                                             1   O        -o-OCH.sub.3                                                                           CH.sub.2 CH(CH.sub.3).sub.2                                                                H                                             1   O       .sub.--m-OCH.sub.3                                                                      H           H                                             1   O       .sub.--m-OCH.sub.3                                                                      CH.sub.3    H                                             1   O       .sub.--m-OCH.sub.3                                                                      CH.sub.2 CH.sub.3                                                                          H                                             1   O       .sub.--m-OCH.sub.3                                                                      CH.sub.2 CH.sub.2 CH.sub.3                                                                 H                                             1   O       .sub.--m-OCH.sub.3                                                                      CH.sub.2 CH.sub.2 CH.sub.2 CH.sub.3                                                        H                                             1   O       .sub.--m-OCH.sub.3                                                                      CH(CH.sub.3).sub.2                                                                         H                                             1   O       .sub.--m-OCH.sub.3                                                                      CH(CH.sub.3)CH.sub.2 CH.sub.3                                                              H                                             1   O       .sub.--m-OCH.sub.3                                                                      CH.sub.2 CH(CH.sub.3).sub.2                                                                H                                             1   S      H         H           H                                             1   S      H         CH.sub.3    H                                             1   S      H         CH.sub.2 CH.sub.3                                                                          H                                             1   S      H         CH.sub.2 CH.sub.2 CH.sub.3                                                                 H                                             1   S      H         CH.sub.2 CH.sub.2 CH.sub.2 CH.sub.3                                                        H                                             1   S      H         CH(CH.sub.3).sub.2                                                                         H                                             1   S      H         CH(CH.sub.3)CH.sub.2 CH.sub.3                                                              H                                             1   S      H         CH.sub.2 CH(CH.sub.3).sub.2                                                                H                                             1   S        -o-Cl   H           H                                             1   S        -o-Cl   CH.sub.3    H                                             1   S        -o-Cl   CH.sub.2 CH.sub.3                                                                          H                                             1   S        -o-Cl   CH.sub.2 CH.sub.2 CH.sub.3                                                                 H                                             1   S         -o-Cl  CH.sub.2 CH.sub.2 CH.sub.2 CH.sub.3                                                        H                                             1   S        -o-Cl   CH(CH.sub.3).sub.2                                                                         H                                             1   S        -o-Cl   CH(CH.sub.3)CH.sub.2 CH.sub.3                                                              H                                             1   S        -o-Cl   CH.sub.2 CH(CH.sub.3).sub.2                                                                H                                             1   S       .sub.--m-Cl                                                                             H           H                                             1   S       .sub.--m-Cl                                                                             CH.sub.3    H                                             1   S       .sub.--m-Cl                                                                             CH.sub.2 CH.sub.3                                                                          H                                             1   S       .sub.--m-Cl                                                                             CH.sub.2 CH.sub.2 CH.sub.3                                                                 H                                             1   S       .sub.--m-Cl                                                                             CH.sub.2 CH.sub.2 CH.sub.2 CH.sub.3                                                        H                                             1   S       .sub.--m-Cl                                                                             CH(CH.sub.3).sub.2                                                                         H                                             1   S       .sub.--m-Cl                                                                             CH(CH.sub.3)CH.sub.2 CH.sub.3                                                              H                                             1   S       .sub.--m-Cl                                                                             CH.sub.2 CH(CH.sub.3).sub.2                                                                H                                             1   S        -o-CH.sub.3                                                                            H           H                                             1   S        -o-CH.sub.3                                                                            CH.sub.3    H                                             1   S       - o-CH.sub.3                                                                            CH.sub.2 CH.sub.3                                                                          H                                             1   S        -o-CH.sub.3                                                                            CH.sub.2 CH.sub.2 CH.sub.3                                                                 H                                             1   S        -o-CH.sub.3                                                                            CH.sub.2 CH.sub.2 CH.sub.2 CH.sub.3                                                        H                                             1   S        -o-CH.sub.3                                                                            CH(CH.sub.3).sub.2                                                                         H                                             1   S        -o-CH.sub.3                                                                            CH(CH.sub.3)CH.sub.2 CH.sub.3                                                              H                                             1   S        -o-CH.sub.3                                                                            CH.sub.2 CH(CH.sub.3).sub.2                                                                H                                             1   S       .sub.--m-CH.sub.3                                                                       H           H                                             1   S       .sub.--m-CH.sub.3                                                                       CH.sub.3    H                                             1   S       .sub.--m-CH.sub.3                                                                       CH.sub.2 CH.sub.3                                                                          H                                             1   S       .sub.--m-CH.sub.3                                                                       CH.sub.2 CH.sub.2 CH.sub.3                                                                 H                                             1   S       .sub.--m-CH.sub.3                                                                       CH.sub.2 CH.sub.2 CH.sub.2 CH.sub.3                                                        H                                             1   S       .sub.--m-CH.sub.3                                                                       CH(CH.sub.3).sub.2                                                                         H                                             1   S       .sub.--m-CH.sub.3                                                                       CH(CH.sub.3)CH.sub.2 CH.sub.3                                                              H                                             1   S       .sub.--m-CH.sub.3                                                                       CH.sub.2 CH(CH.sub.3).sub.2                                                                H                                             1   S        -o-OCH.sub.3                                                                           H           H                                             1   S        -o-OCH.sub.3                                                                           CH.sub.3    H                                             1   S        -o-OCH.sub.3                                                                           CH.sub.2 CH.sub.3                                                                          H                                             1   S        -o-OCH.sub.3                                                                           CH.sub.2 CH.sub.2 CH.sub.3                                                                 H                                             1   S        -o-OCH.sub.3                                                                           CH.sub.2 CH.sub.2 CH.sub.2 CH.sub.3                                                        H                                             1   S        -o-OCH.sub.3                                                                           CH(CH.sub.3).sub.2                                                                         H                                             1   S        -o-OCH.sub.3                                                                           CH(CH.sub.3)CH.sub.2 CH.sub.3                                                              H                                             1   S        -o-OCH.sub.3                                                                           CH.sub.2 CH(CH.sub.3).sub.2                                                                H                                             1   S       .sub.--m-OCH.sub.3                                                                      H           H                                             1   S       .sub.--m-OCH.sub.3                                                                      CH.sub.3    H                                             1   S       .sub.--m-OCH.sub.3                                                                      CH.sub.2 CH.sub.3                                                                          H                                             1   S       .sub.--m-OCH.sub.3                                                                      CH.sub.2 CH.sub.2 CH.sub.3                                                                 H                                             1   S       .sub.--m-OCH.sub.3                                                                      CH.sub.2 CH.sub.2 CH.sub.2 CH.sub.3                                                        H                                             1   S       .sub.--m-OCH.sub.3                                                                      CH(CH.sub.3).sub. 2                                                                        H                                             1   S       .sub.--m-OCH.sub.3                                                                      CH(CH.sub.3)CH.sub.2 CH.sub.3                                                              H                                             1   S       .sub.--m-OCH.sub.3                                                                      CH.sub.2 CH(CH.sub.3).sub.2                                                                H                                             1   SO     H         H           H                                             1   SO     H         CH.sub.3    H                                             1   SO     H         CH.sub.2 CH.sub.3                                                                          H                                             1   SO     H         CH.sub.2 CH.sub.2 CH.sub.3                                                                 H                                             1   SO     H         CH.sub.2 CH.sub.2 CH.sub.2 CH.sub.3                                                        H                                             1   SO     H         CH(CH.sub.3).sub.2                                                                         H                                             1   SO     H         CH(CH.sub.3)CH.sub.2 CH.sub.3                                                              H                                             1   SO     H         CH.sub.2 CH(CH.sub.3).sub.2                                                                H                                             1   SO       -o-Cl   H           H                                             1   SO       -o-Cl   CH.sub.3    H                                             1   SO       -o-Cl   CH.sub.2 CH.sub.3                                                                          H                                             1   SO       -o-Cl   CH.sub.2 CH.sub.2 CH.sub.3                                                                 H                                             1   SO       -o-Cl   CH.sub.2 CH.sub.2 CH.sub.2 CH.sub.3                                                        H                                             1   SO       -o-Cl   CH(CH.sub.3).sub.2                                                                         H                                             1   SO       -o-Cl   CH(CH.sub.3)CH.sub.2 CH.sub.3                                                              H                                             1   SO        -o-Cl  CH.sub.2 CH(CH.sub.3).sub.2                                                                H                                             1   SO      .sub.--m-Cl                                                                             H           H                                             1   SO      .sub.--m-Cl                                                                             CH.sub.3    H                                             1   SO      .sub.--m-Cl                                                                             CH.sub.2 CH.sub.3                                                                          H                                             1   SO      .sub.--m-Cl                                                                             CH.sub.2 CH.sub.2 CH.sub.3                                                                 H                                             1   SO      .sub.--m-Cl                                                                             CH.sub.2 CH.sub.2 CH.sub.2 CH.sub.3                                                        H                                             1   SO      .sub.--m-Cl                                                                             CH(CH.sub.3).sub.2                                                                         H                                             1   SO      .sub.--m-Cl                                                                             CH(CH.sub.3)CH.sub.2 CH.sub.3                                                              H                                             1   SO      .sub.--m-Cl                                                                             CH.sub.2 CH(CH.sub.3).sub.2                                                                H                                             1   SO       -o-CH.sub.3                                                                            H           H                                             1   SO       -o-CH.sub.3                                                                            CH.sub.3    H                                             1   SO       -o-CH.sub.3                                                                            CH.sub.2 CH.sub.3                                                                          H                                             1   SO       -o-CH.sub.3                                                                            CH.sub.2 CH.sub.2 CH.sub.3                                                                 H                                             1   SO       -o-CH.sub.3                                                                            CH.sub.2 CH.sub.2 CH.sub.2 CH.sub.3                                                        H                                             1   SO       -o-CH.sub. 3                                                                           CH(CH.sub.3).sub.2                                                                         H                                             1   SO       -o-CH.sub.3                                                                            CH(CH.sub.3)CH.sub.2 CH.sub.3                                                              H                                             1   SO       -o-CH.sub.3                                                                            CH.sub.2 CH(CH.sub.3).sub.2                                                                H                                             1   SO      .sub.--m-CH.sub.3                                                                       H           H                                             1   SO      .sub.--m-CH.sub.3                                                                       CH.sub.3    H                                             1   SO      .sub.--m-CH.sub.3                                                                       CH.sub.2 CH.sub.3                                                                          H                                             1   SO      .sub.--m-CH.sub.3                                                                       CH.sub.2 CH.sub.2 CH.sub.3                                                                 H                                             1   SO      .sub.--m-CH.sub.3                                                                       CH.sub.2 CH.sub.2 CH.sub.2 CH.sub.3                                                        H                                             1   SO      .sub.--m-CH.sub.3                                                                       CH(CH.sub.3).sub.2                                                                         H                                             1   SO      .sub.--m-CH.sub.3                                                                       CH(CH.sub.3)CH.sub.2 CH.sub.3                                                              H                                             1   SO      .sub.--m-CH.sub.3                                                                       CH.sub.2 CH(CH.sub.3).sub.2                                                                H                                             1   SO       -o-OCH.sub.3                                                                           H           H                                             1   SO       -o-OCH.sub.3                                                                           CH.sub.3    H                                             1   SO       -o-OCH.sub.3                                                                           CH.sub.2 CH.sub.3                                                                          H                                             1   SO       -o-OCH.sub. 3                                                                          CH.sub.2 CH.sub.2 CH.sub.3                                                                 H                                             1   SO       -o-OCH.sub.3                                                                           CH.sub.2 CH.sub.2 CH.sub.2 CH.sub.3                                                        H                                             1   SO       -o-OCH.sub.3                                                                           CH(CH.sub.3).sub.2                                                                         H                                             1   SO       -o-OCH.sub.3                                                                           CH(CH.sub.3)CH.sub.2 CH.sub.3                                                              H                                             1   SO       -o-OCH.sub.3                                                                           CH.sub.2 CH(CH.sub.3).sub.2                                                                H                                             1   SO      .sub.--m-OCH.sub.3                                                                      H           H                                             1   SO      .sub.--m-OCH.sub.3                                                                      CH.sub.3    H                                             1   SO      .sub.--m-OCH.sub.3                                                                      CH.sub.2 CH.sub.3                                                                          H                                             1   SO      .sub.--m-OCH.sub.3                                                                      CH.sub.2 CH.sub.2 CH.sub.3                                                                 H                                             1   SO      .sub.--m-OCH.sub.3                                                                      CH.sub.2 CH.sub.2 CH.sub.2 CH.sub.3                                                        H                                             1   SO      .sub.--m-OCH.sub.3                                                                      CH(CH.sub.3).sub.2                                                                         H                                             1   SO      .sub.--m-OCH.sub.3                                                                      CH(CH.sub.3)CH.sub.2 CH.sub.3                                                              H                                             1   SO      .sub.--m-OCH.sub.3                                                                      CH.sub.2 CH(CH.sub.3).sub.2                                                                H                                             1   SO.sub.2                                                                              H         H           H     238-240                                 1   SO.sub.2                                                                              H         CH.sub.3    H     225-227                                 1   SO.sub.2                                                                              H         CH.sub.3    CH.sub.3                                                                             235-237                                 1   SO.sub.2                                                                              H         CH.sub.2 CH.sub.3                                                                          H                                             1   SO.sub.2                                                                              H         CH.sub.2 CH.sub.2 CH.sub.3                                                                 H                                             1   SO.sub.2                                                                              H         CH.sub.2 CH.sub.2 CH.sub.2 CH.sub.3                                                        H                                             1   SO.sub.2                                                                              H         CH(CH.sub.3).sub.2                                                                         H                                             1   SO.sub.2                                                                              H         CH(CH.sub.3)CH.sub.2 CH.sub.3                                                              H                                             1   SO.sub.2                                                                              H         CH.sub.2 CH(CH.sub.3).sub.2                                                                H                                             1   SO.sub.2                                                                                -o-Cl   H           H                                             1   SO.sub.2                                                                                -o-Cl   CH.sub.3    H                                             1   SO.sub.2                                                                                -o-Cl   CH.sub.3    CH.sub.3                                      1   SO.sub.2                                                                                -o-Cl   CH.sub.2 CH.sub.3                                                                          H                                             1   SO.sub.2                                                                                -o-Cl   CH.sub.2 CH.sub.2 CH.sub.3                                                                 H                                             1   SO.sub.2                                                                                -o-Cl   CH.sub.2 CH.sub.2 CH.sub.2 CH.sub.3                                                        H                                             1   SO.sub.2                                                                                -o-Cl   CH(CH.sub.3).sub.2                                                                         H                                             1   SO.sub.2                                                                                -o-Cl   CH(CH.sub.3)CH.sub.2 CH.sub.3                                                              H                                             1   SO.sub.2                                                                                -o-Cl   CH.sub.2 CH(CH.sub.3).sub.2                                                                H                                             1   SO.sub.2                                                                               .sub.--m-Cl                                                                             H           H                                             1   SO.sub.2                                                                               .sub.--m-Cl                                                                             CH.sub.3    H                                             1   SO.sub.2                                                                               .sub.--m-Cl                                                                             CH.sub.3    CH.sub.3                                      1   SO.sub.2                                                                               .sub.--m-Cl                                                                             CH.sub.2 CH.sub.3                                                                          H                                             1   SO.sub.2                                                                               .sub.--m-Cl                                                                             CH.sub.2 CH.sub.2 CH.sub.3                                                                 H                                             1   SO.sub.2                                                                               .sub.--m-Cl                                                                             CH.sub.2 CH.sub.2 CH.sub.2 CH.sub.3                                                        H                                             1   SO.sub.2                                                                               .sub.--m-Cl                                                                             CH(CH.sub.3).sub.2                                                                         H                                             1   SO.sub.2                                                                               .sub.--m-Cl                                                                             CH(CH.sub.3)CH.sub.2 CH.sub.3                                                              H                                             1   SO.sub.2                                                                               .sub.--m-Cl                                                                             CH.sub.2 CH(CH.sub.3).sub.2                                                                H                                             1   SO.sub.2                                                                                -o-CH.sub.3                                                                            H           H                                             1   SO.sub.2                                                                                -o-CH.sub.3                                                                            CH.sub.3    H                                             1   SO.sub.2                                                                                -o-CH.sub.3                                                                            CH.sub.3    CH.sub.3                                      1   SO.sub.2                                                                                -o-CH.sub.3                                                                            CH.sub.2 CH.sub.3                                                                          H                                             1   SO.sub.2                                                                               -  o-CH.sub.3                                                                           CH.sub.2 CH.sub.2 CH.sub.3                                                                 H                                             1   SO.sub.2                                                                                -o-CH.sub.3                                                                            CH.sub.2 CH.sub.2 CH.sub.2 CH.sub.3                                                        H                                             1   SO.sub.2                                                                                -o-CH.sub.3                                                                            CH(CH.sub.3).sub.2                                                                         H                                             1   SO.sub.2                                                                                -o-CH.sub.3                                                                            CH(CH.sub.3)CH.sub.2 CH.sub.3                                                              H                                             1   SO.sub.2                                                                                -o-CH.sub.3                                                                            CH.sub.2 CH(CH.sub.3).sub.2                                                                H                                             1   SO.sub.2                                                                               .sub.--m-CH.sub.3                                                                       H           H                                             1   SO.sub.2                                                                               .sub.--m-CH.sub.3                                                                       CH.sub.3    H                                             1   SO.sub.2                                                                               .sub.--m-CH.sub.3                                                                       CH.sub.3    CH.sub.3                                      1   SO.sub.2                                                                               .sub.--m-CH.sub.3                                                                       CH.sub.2 CH.sub.3                                                                          H                                             1   SO.sub.2                                                                               .sub.--m-CH.sub.3                                                                       CH.sub.2 CH.sub.2 CH.sub.3                                                                 H                                             1   SO.sub.2                                                                               .sub.--m-CH.sub.3                                                                       CH.sub.2 CH.sub.2 CH.sub.2 CH.sub.3                                                        H                                             1   SO.sub.2                                                                               .sub.--m-CH.sub.3                                                                       CH(CH.sub.3).sub.2                                                                         H                                             1   SO.sub.2                                                                               .sub.--m-CH.sub.3                                                                       CH(CH.sub.3)CH.sub.2 CH.sub.3                                                              H                                             1   SO.sub.2                                                                               .sub.--m-CH.sub.3                                                                       CH.sub.2 CH(CH.sub.3).sub.2                                                                H                                             1   SO.sub.2                                                                                -o-OCH.sub.3                                                                           H           H                                             1   SO.sub.2                                                                                -o-OCH.sub.3                                                                           CH.sub.3    H                                             1   SO.sub.2                                                                                -o-OCH.sub.3                                                                           CH.sub.3    CH.sub.3                                      1   SO.sub.2                                                                                -o-OCH.sub.3                                                                           CH.sub.2 CH.sub.3                                                                          H                                             1   SO.sub.2                                                                                -o-OCH.sub.3                                                                           CH.sub.2 CH.sub.2 CH.sub.3                                                                 H                                             1   SO.sub.2                                                                                -o-OCH.sub.3                                                                           CH.sub.2 CH.sub.2 CH.sub.2 CH.sub.3                                                        H                                             1   SO.sub.2                                                                                -o-OCH.sub.3                                                                           CH(CH.sub.3).sub.2                                                                         H                                             1   SO.sub.2                                                                                -o-OCH.sub.3                                                                           CH(CH.sub.3)CH.sub.2 CH.sub.3                                                              H                                             1   SO.sub.2                                                                                -o-OCH.sub.3                                                                           CH.sub.2 CH(CH.sub.3).sub.2                                                                H                                             1   SO.sub.2                                                                               .sub.--m-OCH.sub.3                                                                      H           H                                             1   SO.sub.2                                                                               .sub.--m-OCH.sub.3                                                                      CH.sub.3    H                                             1   SO.sub.2                                                                               .sub.--m-OCH.sub.3                                                                      CH.sub.3    CH.sub.3                                      1   SO.sub.2                                                                                .sub.--m-OCH.sub.3                                                                     CH.sub.2 CH.sub.3                                                                          H                                             1   SO.sub.2                                                                               .sub.--m-OCH.sub.3                                                                      CH.sub.2 CH.sub.2 CH.sub.3                                                                 H                                             1   SO.sub.2                                                                               .sub.--m-OCH.sub.3                                                                      CH.sub.2 CH.sub.2 CH.sub.2 CH.sub.3                                                        H                                             1   SO.sub.2                                                                               .sub.--m-OCH.sub.3                                                                      CH(CH.sub.3).sub.2                                                                         H                                             1   SO.sub.2                                                                               .sub.--m-OCH.sub.3                                                                      CH(CH.sub.3)CH.sub.2 CH.sub.3                                                              H                                             1   SO.sub.2                                                                               .sub.--m-OCH.sub.3                                                                      CH.sub.2 CH(CH.sub.3).sub.2                                                                H                                             2   O      H         H           H                                             2   O      H         CH.sub.3    H                                             2   O      H         CH.sub.2 CH.sub.3                                                                          H                                             2   O      H         CH.sub.2 CH.sub.2 CH.sub.3                                                                 H                                             2   O      H         CH.sub.2 CH.sub.2 CH.sub.2 CH.sub.3                                                        H                                             2   O      H         CH(CH.sub.3).sub.2                                                                         H                                             2   O      H         CH(CH.sub.3)CH.sub.2 CH.sub.3                                                              H                                             2   O      H         CH.sub.2 CH(CH.sub.3).sub.2                                                                H                                             2   O        -o-Cl   H           H                                             2   O        -o-Cl   CH.sub.3    H                                             2   O        -o-Cl   CH.sub.2 CH.sub.3                                                                          H                                             2   O        -o-Cl   CH.sub.2 CH.sub.2 CH.sub.3                                                                 H                                             2   O        -o-Cl   CH.sub.2 CH.sub.2 CH.sub.2 CH.sub.3                                                        H                                             2   O        -o-Cl   CH(CH.sub.3).sub.2                                                                         H                                             2   O        -o-Cl   CH(CH.sub.3)CH.sub.2 CH.sub.3                                                              H                                             2   O        -o-Cl   CH.sub.2 CH(CH.sub.3).sub.2                                                                H                                             2   O       .sub.--m-Cl                                                                             H           H                                             2   O       .sub.--m-Cl                                                                             CH.sub.3    H                                             2   O       .sub.--m-Cl                                                                             CH.sub.2 CH.sub.3                                                                          H                                             2   O       .sub.--m-Cl                                                                             CH.sub.2 CH.sub.2 CH.sub.3                                                                 H                                             2   O       .sub.--m-Cl                                                                             CH.sub.2 CH.sub.2 CH.sub.2 CH.sub.3                                                        H                                             2   O       .sub.--m-Cl                                                                             CH(CH.sub.3).sub.2                                                                         H                                             2   O       .sub.--m-Cl                                                                             CH(CH.sub.3)CH.sub.2 CH.sub.3                                                              H                                             2   O       .sub.--m-Cl                                                                             CH.sub.2 CH(CH.sub.3).sub.2                                                                H                                             2   O        -o-CH.sub.3                                                                            H           H                                             2   O        - o-CH.sub.3                                                                           CH.sub.3    H                                             2   O        -o-CH.sub.3                                                                            CH.sub.2 CH.sub.3                                                                          H                                             2   O        -o-CH.sub.3                                                                            CH.sub.2 CH.sub.2 CH.sub.3                                                                 H                                             2   O        -o-CH.sub.3                                                                            CH.sub.2 CH.sub.2 CH.sub.2 CH.sub.3                                                        H                                             2   O        -o-CH.sub.3                                                                            CH(CH.sub.3).sub.2                                                                         H                                             2   O        -o-CH.sub.3                                                                            CH(CH.sub.3)CH.sub.2 CH.sub.3                                                              H                                             2   O        -o-CH.sub.3                                                                            CH.sub.2 CH(CH.sub.3).sub.2                                                                H                                             2   O       .sub.--m-CH.sub.3                                                                       H           H                                             2   O       .sub.--m-CH.sub.3                                                                       CH.sub.3    H                                             2   O       .sub.--m-CH.sub.3                                                                       CH.sub.2 CH.sub.3                                                                          H                                             2   O       .sub.--m-CH.sub.3                                                                       CH.sub.2 CH.sub.2 CH.sub.3                                                                 H                                             2   O       .sub.--m-CH.sub.3                                                                       CH.sub.2 CH.sub.2 CH.sub.2 CH.sub.3                                                        H                                             2   O       .sub.--m-CH.sub.3                                                                       CH(CH.sub.3).sub.2                                                                         H                                             2   O       .sub.--m-CH.sub.3                                                                       CH(CH.sub.3)CH.sub.2 CH.sub.3                                                              H                                             2   O       .sub.--m-CH.sub.3                                                                       CH.sub.2 CH(CH.sub.3).sub.2                                                                H                                             2   O        -o-OCH.sub.3                                                                           H           H                                             2   O        -o-OCH.sub.3                                                                           CH.sub.3    H                                             2   O        -o-OCH.sub.3                                                                           CH.sub.2 CH.sub.3                                                                          H                                             2   O        -o-OCH.sub.3                                                                           CH.sub.2 CH.sub.2 CH.sub.3                                                                 H                                             2   O        -o-OCH.sub.3                                                                           CH.sub.2 CH.sub.2 CH.sub.2 CH.sub.3                                                        H                                             2   O        -o-OCH.sub.3                                                                           CH(CH.sub.3).sub.2                                                                         H                                             2   O        -o-OCH.sub.3                                                                           CH(CH.sub.3)CH.sub.2 CH.sub.3                                                              H                                             2   O        -o-OCH.sub.3                                                                           CH.sub.2 CH(CH.sub.3).sub.2                                                                H                                             2   O       .sub.--m-OCH.sub.3                                                                      H           H                                             2   O       .sub.--m-OCH.sub.3                                                                      CH.sub.3    H                                             2   O       .sub.--m-OCH.sub.3                                                                      CH.sub.2 CH.sub.3                                                                          H                                             2   O       .sub.--m-OCH.sub.3                                                                      CH.sub.2 CH.sub.2 CH.sub.3                                                                 H                                             2   O       .sub.--m-OCH.sub.3                                                                      CH.sub.2 CH.sub.2 CH.sub.2 CH.sub.3                                                        H                                             2   O       .sub.--m-OCH.sub.3                                                                      CH(CH.sub.3).sub.2                                                                         H                                             2   O       .sub.--m-OCH.sub.3                                                                      CH(CH.sub.3)CH.sub.2 CH.sub.3                                                              H                                             2   O       .sub.--m-OCH.sub.3                                                                      CH.sub.2 CH(CH.sub.3).sub.2                                                                H                                             2   S      H         H           H                                             2   S      H         CH.sub.3    H                                             2   S      H         CH.sub.2 CH.sub.3                                                                          H                                             2   S      H         CH.sub.2 CH.sub.2 CH.sub.3                                                                 H                                             2   S      H         CH.sub.2 CH.sub.2 CH.sub.2 CH.sub.3                                                        H                                             2   S      H         CH(CH.sub.3).sub.2                                                                         H                                             2   S      H         CH(CH.sub.3)CH.sub.2 CH.sub.3                                                              H                                             2   S      H         CH.sub.2 CH(CH.sub.3).sub.2                                                                H                                             2   S        -o-Cl   H           H                                             2   S        -o-Cl   CH.sub.3    H                                             2   S        -o-Cl   CH.sub.2 CH.sub.3                                                                          H                                             2   S        -o-Cl   CH.sub.2 CH.sub.2 CH.sub.3                                                                 H                                             2   S        -o-Cl   CH.sub.2 CH.sub.2 CH.sub.2 CH.sub.3                                                        H                                             2   S        -o-Cl   CH(CH.sub.3).sub.2                                                                         H                                             2   S        -o-Cl   CH(CH.sub.3)CH.sub.2 CH.sub.3                                                              H                                             2   S        -o-Cl   CH.sub.2 CH(CH.sub.3).sub.2                                                                H                                             2   S       .sub.--m-Cl                                                                             H           H                                             2   S       .sub.--m-Cl                                                                             CH.sub.3    H                                             2   S       .sub.--m-Cl                                                                             CH.sub.2 CH.sub.3                                                                          H                                             2   S       .sub.--m-Cl                                                                             CH.sub.2 CH.sub.2 CH.sub.3                                                                 H                                             2   S       .sub.--m-Cl                                                                             CH.sub.2 CH.sub.2 CH.sub.2 CH.sub.3                                                        H                                             2   S       .sub.--m-Cl                                                                             CH(CH.sub.3).sub.2                                                                         H                                             2   S       .sub.--m-Cl                                                                             CH(CH.sub.3)CH.sub.2 CH.sub.3                                                              H                                             2   S       .sub.--m-Cl                                                                             CH.sub.2 CH(CH.sub.3).sub.2                                                                H                                             2   S        -o-CH.sub.3                                                                            H           H                                             2   S        -o-CH.sub.3                                                                            CH.sub.3    H                                             2   S        -o-CH.sub.3                                                                            CH.sub.2 CH.sub.3                                                                          H                                             2   S        -o-CH.sub.3                                                                            CH.sub.2 CH.sub.2 CH.sub.3                                                                 H                                             2   S        -o-CH.sub.3                                                                            CH.sub.2 CH.sub.2 CH.sub.2 CH.sub.3                                                        H                                             2   S        -o-CH.sub.3                                                                            CH(CH.sub.3).sub.2                                                                         H                                             2   S        -o-CH.sub.3                                                                            CH(CH.sub.3)CH.sub.2 CH.sub.3                                                              H                                             2   S        -o-CH.sub.3                                                                            CH.sub.2 CH(CH.sub.3).sub.2                                                                H                                             2   S       .sub.--m-CH.sub.3                                                                       H           H                                             2   S       .sub.--m-CH.sub.3                                                                       CH.sub.3    H                                             2   S       .sub.--m-CH.sub.3                                                                       CH.sub.2 CH.sub.3                                                                          H                                             2   S       .sub.--m-CH.sub.3                                                                       CH.sub.2 CH.sub.2 CH.sub.3                                                                 H                                             2   S       .sub.--m-CH.sub.3                                                                       CH.sub.2 CH.sub.2 CH.sub.2 CH.sub.3                                                        H                                             2   S       .sub.--m-CH.sub.3                                                                       CH(CH.sub.3).sub.2                                                                         H                                             2   S       .sub.--m-CH.sub.3                                                                       CH(CH.sub.3)CH.sub.2 CH.sub.3                                                              H                                             2   S       .sub.--m-CH.sub.3                                                                       CH.sub.2 CH(CH.sub.3).sub.2                                                                H                                             2   S        -o-OCH.sub.3                                                                           H           H                                             2   S        -o-OCH.sub.3                                                                           CH.sub.3    H                                             2   S        -o-OCH.sub.3                                                                           CH.sub.2 CH.sub.3                                                                          H                                             2   S        -o-OCH.sub.3                                                                           CH.sub.2 CH.sub.2 CH.sub.3                                                                 H                                             2   S        -o-OCH.sub.3                                                                           CH.sub.2 CH.sub.2 CH.sub.2 CH.sub.3                                                        H                                             2   S        -o-OCH.sub.3                                                                           CH(CH.sub.3).sub.2                                                                         H                                             2   S        -o-OCH.sub.3                                                                           CH(CH.sub.3)CH.sub.2 CH.sub.3                                                              H                                             2   S        -o-OCH.sub.3                                                                           CH.sub.2 CH(CH.sub.3).sub.2                                                                H                                             2   S       .sub.--m-OCH.sub.3                                                                      H           H                                             2   S       .sub.--m-OCH.sub.3                                                                      CH.sub.3    H                                             2   S       .sub.--m-OCH.sub.3                                                                      CH.sub.2 CH.sub.3                                                                          H                                             2   S       .sub.--m-OCH.sub.3                                                                      CH.sub.2 CH.sub.2 CH.sub.3                                                                 H                                             2   S       .sub.--m-OCH.sub.3                                                                      CH.sub.2 CH.sub.2 CH.sub.2 CH.sub.3                                                        H                                             2   S       .sub.--m-OCH.sub.3                                                                      CH(CH.sub.3).sub.2                                                                         H                                             2   S       .sub.--m-OCH.sub.3                                                                      CH(CH.sub.3)CH.sub.2 CH.sub.3                                                              H                                             2   S       .sub.--m-OCH.sub.3                                                                      CH.sub. 2 CH(CH.sub.3).sub.2                                                               H                                             2   SO     H         H           H                                             2   SO     H         CH.sub.3    H                                             2   SO     H         CH.sub.2 CH.sub.3                                                                          H                                             2   SO     H         CH.sub.2 CH.sub.2 CH.sub.3                                                                 H                                             2   SO     H         CH.sub.2 CH.sub.2 CH.sub.2 CH.sub.3                                                        H                                             2   SO     H         CH(CH.sub.3).sub.2                                                                         H                                             2   SO     H         CH(CH.sub.3)CH.sub.2 CH.sub.3                                                              H                                             2   SO     H         CH.sub.2 CH(CH.sub.3).sub.2                                                                H                                             2   SO       -o-Cl   H           H                                             2   SO       -o-Cl   CH.sub.3    H                                             2   SO       -o-Cl   CH.sub.2 CH.sub.3                                                                          H                                             2   SO       -o-Cl   CH.sub.2 CH.sub.2 CH.sub.3                                                                 H                                             2   SO       -o-Cl   CH.sub.2 CH.sub.2 CH.sub.2 CH.sub.3                                                        H                                             2   SO       -o-Cl   CH(CH.sub.3).sub.2                                                                         H                                             2   SO       -o-Cl   CH(CH.sub.3)CH.sub.2 CH.sub.3                                                              H                                             2   SO       -o-Cl   CH.sub.2 CH(CH.sub.3).sub.2                                                                H                                             2   SO      .sub.--m-Cl                                                                             H           H                                             2   SO      .sub.-- m-Cl                                                                            CH.sub.3    H                                             2   SO      .sub.--m-Cl                                                                             CH.sub.2 CH.sub.3                                                                          H                                             2   SO      .sub.--m-Cl                                                                             CH.sub.2 CH.sub.2 CH.sub.3                                                                 H                                             2   SO      .sub.--m-Cl                                                                             CH.sub.2 CH.sub.2 CH.sub.2 CH.sub.3                                                        H                                             2   SO      .sub.--m-Cl                                                                             CH(CH.sub.3).sub.2                                                                         H                                             2   SO      .sub.--m-Cl                                                                             CH(CH.sub.3)CH.sub.2 CH.sub.3                                                              H                                             2   SO      .sub.--m-Cl                                                                             CH.sub.2 CH(CH.sub.3).sub.2                                                                H                                             2   SO       -o-CH.sub.3                                                                            H           H                                             2   SO       -o-CH.sub.3                                                                            CH.sub.3    H                                             2   SO       -o-CH.sub.3                                                                            CH.sub.2 CH.sub.3                                                                          H                                             2   SO       -o-CH.sub.3                                                                            CH.sub.2 CH.sub.2 CH.sub.3                                                                 H                                             2   SO       -o-CH.sub.3                                                                            CH.sub.2 CH.sub.2 CH.sub.2 CH.sub.3                                                        H                                             2   SO       -o-CH.sub.3                                                                            CH(CH.sub.3).sub.2                                                                         H                                             2   SO       -o-CH.sub.3                                                                            CH(CH.sub.3)CH.sub.2 CH.sub.3                                                              H                                             2   SO       - o-CH.sub.3                                                                           CH.sub.2 CH(CH.sub.3).sub.2                                                                H                                             2   SO      .sub.--m-CH.sub.3                                                                       H           H                                             2   SO      .sub.--m-CH.sub.3                                                                       CH.sub.3    H                                             2   SO      .sub.--m-CH.sub.3                                                                       CH.sub.2 CH.sub.3                                                                          H                                             2   SO      .sub.--m-CH.sub.3                                                                       CH.sub.2 CH.sub.2 CH.sub.3                                                                 H                                             2   SO      .sub.--m-CH.sub.3                                                                       CH.sub.2 CH.sub.2 CH.sub.2 CH.sub.3                                                        H                                             2   SO      .sub.--m-CH.sub.3                                                                       CH(CH.sub.3).sub.2                                                                         H                                             2   SO      .sub.--m-CH.sub.3                                                                       CH(CH.sub.3)CH.sub.2 CH.sub.3                                                              H                                             2   SO      .sub.--m-CH.sub.3                                                                       CH.sub.2 CH(CH.sub.3).sub.2                                                                H                                             2   SO       -o-OCH.sub.3                                                                           H           H                                             2   SO       -o-OCH.sub.3                                                                           CH.sub.3    H                                             2   SO       -o-OCH.sub.3                                                                           CH.sub.2 CH.sub.3                                                                          H                                             2   SO       -o-OCH.sub.3                                                                           CH.sub.2 CH.sub.2 CH.sub.3                                                                 H                                             2   SO       -o-OCH.sub.3                                                                           CH.sub.2 CH.sub.2 CH.sub.2 CH.sub.3                                                        H                                             2   SO       -o-OCH.sub.3                                                                           CH(CH.sub.3).sub.2                                                                         H                                             2   SO       -o-OCH.sub.3                                                                           CH(CH.sub.3)CH.sub.2 CH.sub.3                                                              H                                             2   SO       -o-OCH.sub.3                                                                           CH.sub.2 CH(CH.sub.3).sub.2                                                                H                                             2   SO      .sub.--m-OCH.sub.3                                                                      H           H                                             2   SO      .sub.--m-OCH.sub.3                                                                      CH.sub.3    H                                             2   SO      .sub.--m-OCH.sub.3                                                                      CH.sub.2 CH.sub.3                                                                          H                                             2   SO      .sub.--m-OCH.sub.3                                                                      CH.sub.2 CH.sub.2 CH.sub.3                                                                 H                                             2   SO      .sub.--m-OCH.sub.3                                                                      CH.sub.2 CH.sub.2 CH.sub.2 CH.sub.3                                                        H                                             2   SO      .sub.--m-OCH.sub.3                                                                      CH(CH.sub.3).sub.2                                                                         H                                             2   SO      .sub.--m-OCH.sub.3                                                                      CH(CH.sub.3)CH.sub.2 CH.sub.3                                                              H                                             2   SO      .sub.--m-OCH.sub.3                                                                      CH.sub.2 CH(CH.sub.3).sub.2                                                                H                                             2   SO.sub.2                                                                              H         H           H                                             2   SO.sub.2                                                                              H         CH.sub.3    H                                             2   SO.sub.2                                                                              H         CH.sub.3    CH.sub.3                                      2   SO.sub.2                                                                              H         CH.sub.2 CH.sub.3                                                                          H                                             2   SO.sub.2                                                                              H         CH.sub.2 CH.sub.2 CH.sub. 3                                                                H                                             2   SO.sub.2                                                                              H         CH.sub.2 CH.sub.2 CH.sub.2 CH.sub.3                                                        H                                             2   SO.sub.2                                                                              H         CH(CH.sub.3).sub.2                                                                         H                                             2   SO.sub.2                                                                              H         CH(CH.sub.3)CH.sub.2 CH.sub.3                                                              H                                             2   SO.sub.2                                                                              H         CH.sub.2 CH(CH.sub.3).sub.2                                                                H                                             2   SO.sub.2                                                                                -o-Cl   H           H                                             2   SO.sub.2                                                                                -o-Cl   CH.sub.3    H                                             2   SO.sub.2                                                                                -o-Cl   CH.sub.3    CH.sub.3                                      2   SO.sub.2                                                                                -o-Cl   CH.sub.2 CH.sub.3                                                                          H                                             2   SO.sub.2                                                                                -o-Cl   CH.sub.2 CH.sub.2 CH.sub.3                                                                 H                                             2   SO.sub.2                                                                                -o-Cl   CH.sub.2 CH.sub.2 CH.sub.2 CH.sub.3                                                        H                                             2   SO.sub.2                                                                                -o-Cl   CH(CH.sub.3).sub.2                                                                         H                                             2   SO.sub.2                                                                                -o-Cl   CH(CH.sub.3)CH.sub.2 CH.sub.3                                                              H                                             2   SO.sub.2                                                                                -o-Cl   CH.sub.2 CH(CH.sub.3).sub.2                                                                H                                             2   SO.sub.2                                                                               .sub.--m-Cl                                                                             H           H                                             2   SO.sub.2                                                                               .sub.--m-Cl                                                                             CH.sub.3    H                                             2   SO.sub.2                                                                               .sub.--m-Cl                                                                             CH.sub.3    CH.sub.3                                      2   SO.sub.2                                                                               .sub.--m-Cl                                                                             CH.sub.2 CH.sub.3                                                                          H                                             2   SO.sub.2                                                                               .sub.--m-Cl                                                                             CH.sub.2 CH.sub.2 CH.sub.3                                                                 H                                             2   SO.sub.2                                                                               .sub.--m-Cl                                                                             CH.sub.2 CH.sub.2 CH.sub.2 CH.sub.3                                                        H                                             2   SO.sub.2                                                                               .sub.--m-Cl                                                                             CH(CH.sub.3).sub.2                                                                         H                                             2   SO.sub.2                                                                               .sub.--m-Cl                                                                             CH(CH.sub.3)CH.sub.2 CH.sub.3                                                              H                                             2   SO.sub.2                                                                               .sub.--m-Cl                                                                             CH.sub.2 CH(CH.sub.3).sub.2                                                                H                                             2   SO.sub.2                                                                                -o-CH.sub.3                                                                            H           H                                             2   SO.sub.2                                                                                -o-CH.sub.3                                                                            CH.sub.3    H                                             2   SO.sub.2                                                                                -o-CH.sub.3                                                                            CH.sub.3    CH.sub.3                                      2   SO.sub.2                                                                                -o-CH.sub.3                                                                            CH.sub.2 CH.sub.3                                                                          H                                             2   SO.sub.2                                                                                -o-CH.sub.3                                                                            CH.sub.2 CH.sub.2 CH.sub.3                                                                 H                                             2   SO.sub.2                                                                                -o-CH.sub.3                                                                            CH.sub.2 CH.sub.2 CH.sub.2 CH.sub.3                                                        H                                             2   SO.sub.2                                                                                 -o-CH.sub.3                                                                           CH(CH.sub.3).sub.2                                                                         H                                             2   SO.sub.2                                                                                -o-CH.sub.3                                                                            CH(CH.sub.3)CH.sub.2 CH.sub.3                                                              H                                             2   SO.sub.2                                                                                -o-CH.sub.3                                                                            CH.sub.2 CH(CH.sub.3).sub.2                                                                H                                             2   SO.sub.2                                                                               .sub.--m-CH.sub.3                                                                       H           H                                             2   SO.sub.2                                                                               .sub.--m-CH.sub.3                                                                       CH.sub.3    H                                             2   SO.sub.2                                                                               .sub.--m-CH.sub.3                                                                       CH.sub.3    CH.sub.3                                      2   SO.sub.2                                                                               .sub.--m-CH.sub.3                                                                       CH.sub.2 CH.sub.3                                                                          H                                             2   SO.sub.2                                                                               .sub.--m-CH.sub.3                                                                       CH.sub.2 CH.sub.2 CH.sub.3                                                                 H                                             2   SO.sub.2                                                                               .sub.--m-CH.sub.3                                                                       CH.sub.2 CH.sub.2 CH.sub.2 CH.sub.3                                                        H                                             2   SO.sub.2                                                                               .sub.--m-CH.sub.3                                                                       CH(CH.sub.3).sub.2                                                                         H                                             2   SO.sub.2                                                                               .sub.--m-CH.sub.3                                                                       CH(CH.sub.3)CH.sub.2 CH.sub.3                                                              H                                             2   SO.sub.2                                                                               .sub.--m-CH.sub.3                                                                       CH.sub.2 CH(CH.sub.3).sub.2                                                                H                                             2   SO.sub.2                                                                                -o-OCH.sub.3                                                                           H           H                                             2   SO.sub.2                                                                                 -o-OCH.sub.3                                                                          CH.sub.3    H                                             2   SO.sub.2                                                                                -o-OCH.sub.3                                                                           CH.sub.3    CH.sub.3                                      2   SO.sub.2                                                                                -o-OCH.sub.3                                                                           CH.sub.2 CH.sub.3                                                                          H                                             2   SO.sub.2                                                                                -o-OCH.sub.3                                                                           CH.sub.2 CH.sub.2 CH.sub.3                                                                 H                                             2   SO.sub.2                                                                                -o-OCH.sub.3                                                                           CH.sub.2 CH.sub.2 CH.sub.2 CH.sub.3                                                        H                                             2   SO.sub.2                                                                                -o-OCH.sub.3                                                                           CH(CH.sub.3).sub.2                                                                         H                                             2   SO.sub.2                                                                                -o-OCH.sub.3                                                                           CH(CH.sub.3)CH.sub.2 CH.sub.3                                                              H                                             2   SO.sub.2                                                                                -o-OCH.sub.3                                                                           CH.sub.2 CH(CH.sub.3).sub.2                                                                H                                             2   SO.sub.2                                                                               .sub.--m-OCH.sub.3                                                                      H           H                                             2   SO.sub.2                                                                               .sub.--m-OCH.sub.3                                                                      CH.sub.3    H                                             2   SO.sub.2                                                                               .sub.--m-OCH.sub.3                                                                      CH.sub.3    CH.sub.3                                      2   SO.sub.2                                                                               .sub.--m-OCH.sub.3                                                                      CH.sub.2 CH.sub.3                                                                          H                                             2   SO.sub.2                                                                               .sub.--m-OCH.sub.3                                                                      CH.sub.2 CH.sub.2 CH.sub.3                                                                 H                                             2   SO.sub.2                                                                               .sub. --m-OCH.sub.3                                                                     CH.sub.2 CH.sub.2 CH.sub.2 CH.sub.3                                                        H                                             2   SO.sub.2                                                                               .sub.--m-OCH.sub.3                                                                      CH(CH.sub.3).sub.2                                                                         H                                             2   SO.sub.2                                                                               .sub.--m-OCH.sub.3                                                                      CH(CH.sub.3)CH.sub.2 CH.sub.3                                                              H                                             2   SO.sub.2                                                                               .sub.--m-OCH.sub.3                                                                      CH.sub.2 CH(CH.sub.3).sub.2                                                                H                                             ______________________________________                                    

                  TABLE II                                                         ______________________________________                                          ##STR16##                                                                             R.sub.1       R.sub.4                                                  ______________________________________                                                 H             H                                                                H             CH.sub.3                                                          .sub.-o-Cl   H                                                                 .sub.-o-Cl   CH.sub.3                                                          .sub.--m-Cl  H                                                                 .sub.--m-Cl  CH.sub.3                                                          .sub.-o-CH.sub.3                                                                            H                                                                 .sub.-o-CH.sub.3                                                                            CH.sub.3                                                          .sub.--m-CH.sub.3                                                                           H                                                                 .sub.--m-CH.sub.3                                                                           CH.sub.3                                                          .sub.-o-OCH.sub.3                                                                           H                                                                 .sub.-o-OCH.sub.3                                                                           CH.sub.3                                                          .sub.--m-OCH.sub.3                                                                          H                                                                 .sub.--m-OCH.sub.3                                                                          CH.sub.3                                                 ______________________________________                                    

FORMULATIONS

Useful formulations of the compounds of Formula I can be prepared in conventional ways. They include dusts, granules, pellets, solutions, suspensions, emulsions, wettable powders, emulsifiable concentrates and the like. Many of these may be applied directly. Sprayable formulations can be extended in suitable media and used at spray volumes of from a few pints to several hundred gallons per acre. High strength compositions are primarily used as intermediates for further formulation. The formulations, broadly, contain about 1% to 99% by weight of active ingredient(s) and at least one of (a) about 0.1% to 20% surfactant(s) and (b) about 5% to 99% solid or liquid diluent(s). More specifically, they will contain these ingredients in the following approximate proportions:

    ______________________________________                                                     Active  Percent by Weight                                                      Ingredient                                                                             Diluent(s)                                                                               Surfactant(s)                                    ______________________________________                                         Wettable Powders                                                                             20-90      0-74      1-10                                        Oil Suspensions,                                                                              5-50     40-95      0-15                                        Emulsions, Solutions,                                                          (including Emulsifiable                                                        Concentrates)                                                                  Aqueous Suspension                                                                           10-50     40-84      1-20                                        Dusts          1-25     70-99     0-5                                          Granules and Pellets                                                                          1-95      5-99      0-15                                        High Strength 90-99      0-10     0-2                                          Compositions                                                                   ______________________________________                                    

Lower or higher levels of active ingredient can, of course, be present depending on the intended use and the physical properties of the compound. Higher ratios of surfactant to active ingredient are sometimes desirable, and are achieved by incorporation into the formulation or by tank mixing.

Typical solid diluents are described in Watkins, et al., "Handbook of Insecticide Dust Diluents and Carriers", 2nd Ed., Dorland Books, Caldwell, N.J., but other solids, either mined or manufactured, may be used. The more absorptive diluents are preferred for wettable powders and the denser ones for dusts. Typical liquid diluents and solvents are described in Marsden, "Solvents Guide," 2nd Ed., Interscience, New York, 1950. Solubility under 0.1% is preferred for suspension concentrates; solution concentrates are preferably stable against phase separation at 0° C. "McCutcheon's Detergents and Emulsifiers Annual", MC Publishing Corp., Ridgewood, N.J., as well as Sisely and Wood, "Encyclopedia of Surface Active Agents", Chemical Publishing Co., Inc., New York, 1964, list surfactants and recommended uses. All formulations can contain minor amounts of additives to reduce foam, corrosion, microbiological growth, etc. Preferably, ingredients should be approved by the U.S. Environmental Protection Agency for the use intended.

The methods of making such compositions are well known. Solutions are prepared by simply mixing the ingredients. Fine solid compositions are made by blending and, usually, grinding as in a hammer or fluid energy mill. Suspensions are prepared by wet milling (see, for example, Littler, U.S. Pat. No. 3,060,084). Granules and pellets may be made by spraying the active material upon preformed granular carriers or by agglomeration techniques. See J. E. Browning, "Agglomeration", Chemical Engineering, Dec. 4, 1967, pp. 147ff. and "Perry's Chemical Engineer's Handbook", 4th Ed., McGraw-Hill, New York, 1963, pp. 8-59ff.

For further information regarding the art of formulation, see for example:

H. M. Loux, U.S. Pat. No. 3,235,361, Feb. 15, 1966, Col. 6, line 16 through Col. 7, line 19 and Examples 10 through 41;

R. W. Luckenbaugh, U.S. Pat. No. 3,309,192, Mar. 14, 1967, Col. 5, line 43 through Col. 7, line 62 and Examples 8, 12, 15, 39, 41, 52, 53, 58, 132, 138-40, 162-164, 166, 167 and 169-182;

H. Gysin and E. Knusli, U.S. Pat. No. 2,891,855, June 23, 1959, Col. 3, line 66 through Col. 5, line 17 and Examples 1-4;

G. C. Klingman, "Weed Control as a Science", John Wiley and Sons, Inc., New York, 1961, pp. 81-96;

J. D. Fryer and S. A. Evans, "Weed Control Handbook", 5th Ed., Blackwell Scientific Publications, Oxford, 1968, pp. 101-103;

J. B. Buchanan, U.S. Pat. No. 3,576,834, Apr. 27, 1971, Col. 5, Line 36 through Col. 7, Line 70 and Examples 1-4, 17, 106, 123-140;

R. R. Shaffer, U.S. Pat. No. 3,560,616, Feb. 2, 1971, Col. 3, Line 48 through Col. 7, Line 26 and Examples 3-9, 11-18; and

E. Somers, "Formulation", Chapter 6 in Torgeson, "Fungicides", Vol. I, Academic Press, New York, 1967.

In the following examples, all parts are by weight unless otherwise indicated.

EXAMPLE 2 High Strength Concentrate

    ______________________________________                                         N--[(4-bromo-6-methoxypyrimidin-2-yl)aminocarbonyl]-                                                        99%                                               2,3-dihydrobenzo[b]thiophene-7-sulfonamide, 1,1-                               dioxide                                                                        silica aerogel               0.5%                                              synthetic amorphous silica   0.5%                                              ______________________________________                                    

The ingredients are blended and ground in a hammer-mill to produce a material essentially all passing a U.S.S. No. 50 screen (0.3 mm opening). The concentrate may be formulated further if necessary.

EXAMPLE 3 Wettable Powder

    ______________________________________                                         N--[(4-bromo-6-methoxypyrimidin-2-yl)aminocarbonyl]-                                                        90%                                               2,3-dihydrobenzo[b]thiophene-7-sulfonamide, 1,1-                               dioxide                                                                        dioctyl sodium sulfosuccinate                                                                               0.1%                                              synthetic fine silica        9.9%                                              ______________________________________                                    

The ingredients are blended and ground in a hammer-mill to produce particles essentially all below 100 microns. The material is sifted through a U.S.S. No. 50 screen and then packaged.

EXAMPLE 4 Wettable Powder

    ______________________________________                                         N--[(4-bromo-6-methoxypyrimidin-2-yl)aminocarbonyl]-                                                        40%                                               2,3-dihydro-2-methylbenzo[b]thiophene-7-sulfonamide,                           1,1-dioxide                                                                    sodium ligninsulfonate       20%                                               montmorillonite clay         40%                                               ______________________________________                                    

The ingredients are thoroughly blended, coarsely hammer-milled and then air-milled to produce particles essentially all below 10 microns in size. The material is reblended and then packaged.

EXAMPLE 5 Granule

    ______________________________________                                         Wettable Powder of Example 4                                                                         5%                                                       attapulgite granules 95%                                                       (U.S.S. 20-40 mesh; 0.84-0.42 mm)                                              ______________________________________                                    

A slurry of wettable powder containing ≈25% solids is sprayed on the surface of attapulgite granules in a double-cone blender. The granules are dried and packaged.

EXAMPLE 6 Low Strength Granule

    ______________________________________                                         N--[(4-bromo-6-methoxypyrimidin-2-yl)aminocarbonyl]-                                                         1%                                               2,3-dihydrobenzo[b]thiophene-7-sulfonamide, 1,1-                               dioxide                                                                        N,N--dimethylformamide        9%                                               attapulgite granules         90%                                               (U.S.S. 20-40 sieve)                                                           ______________________________________                                    

The active ingredient is dissolved in the solvent and the solution is sprayed upon dedusted granules in a double cone blender. After spraying of the solution has been completed, the blender is allowed to run for a short period and then the granules are packaged.

EXAMPLE 7 Granule

    ______________________________________                                         N--[(4-bromo-6-methoxypyrimidin-2-yl)aminocarbonyl]-                                                        80%                                               2,3-dihydro-2-methylbenzo[b]thiophene-7-sulfonamide,                           1,1-dioxide                                                                    wetting agent                 1%                                               crude ligninsulfonate salt (containing                                                                      10%                                               5-20% of the natural sugars)                                                   attapulgite clay              9%                                               ______________________________________                                    

The ingredients are blended and milled to pass through a 100 mesh screen. This material is then added to a fluid bed granulator, the air flow is adjusted to gently fluidize the material, and a fine spray of water is sprayed onto the fluidized material. The fluidization and spraying are continued until granules of the desired size range are made. The spraying is stopped, but fluidization is continued, optionally with heat, until the water content is reduced to the desired level, generally less than 1%. The material is then discharged, screened to the desired size range, generally 14-100 mesh (1410-149 microns), and packaged for use.

EXAMPLE 8 Extruded Pellet

    ______________________________________                                         N--[(4-bromo-6-methoxypyrimidin-2-yl)aminocarbonyl]-                                                        25%                                               2,3-dihydrobenzo[b]thiophene-7-sulfonamide, 1,1-                               dioxide                                                                        anhydrous sodium sulfate     10%                                               crude calcium ligninsulfonate                                                                                5%                                               sodium alkylnaphthalenesulfonate                                                                             1%                                               calcium/magnesium bentonite  59%                                               ______________________________________                                    

The ingredients are blended, hammer-milled and then moistened with about 12% water. The mixture is extruded as cylinders about 3 mm diameter which are cut to produde pellets about 3 mm long. These may be used directly after drying, or the dried pellets may be crushed to pass a U.S.S. No. 20 sieve (0.84 mm openings). The granules held on a U.S.S. No. 40 sieve (0.42 mm openings) may be packaged for use and the fines recycled.

EXAMPLE 9 Dust

    ______________________________________                                         N--[(4-bromo-6-methoxypyrimidin-2-yl)aminocarbonyl]-                                                        10%                                               2,3-dihydrobenzo[b]thiophene-7-sulfonamide, 1,1-                               dioxide                                                                        attapulgite                  10%                                               talc                         80%                                               ______________________________________                                    

The active ingredient is blended with attapulgite and then passed through a hammer-mill to produce particles substantially all below 200 microns. The ground concentrate is then blended with powdered talc until homogeneous.

EXAMPLE 10 Oil Suspension

    ______________________________________                                         N--[(4-bromo-6-methoxypyrimidin-2-yl)aminocarbonyl]-                                                        35%                                               2,3-dihydrobenzo[b]thiophene-7-sulfonamide, 1,1-                               dioxide                                                                        blend of polyalcohol carboxylic                                                                              6%                                               esters and oil soluble petroleum                                               sulfonates                                                                     xylene                       59%                                               ______________________________________                                    

The ingredients are combined and ground together in a sand mill to produce particles essentially all below 5 microns. The product can be used directly, extended with oils, or emulsified in water.

EXAMPLE 11 Aqueous Suspension

    ______________________________________                                         N--[(4-bromo-6-methoxypyrimidin-2-yl)aminocarbonyl]-                                                         40%                                              2,3-dihydro-2-methylbenzo[b]thiophene-7-sulfonamide,                           1,1-dioxide                                                                    polyacrylic acid thickener   0.3%                                              dodecylphenol polyethylene glycol ether                                                                     0.5%                                              disodium phosphate             1%                                              monosodium phosphate         0.5%                                              polyvinyl alcohol            1.0%                                              water                        56.7%                                             ______________________________________                                    

The ingredients are blended and ground together in a sand mill to produce particles essentially all under 5 microns in size.

EXAMPLE 12 Solution

    ______________________________________                                         N--[(4-bromo-6-methoxypyrimidin-2-yl)aminocarbonyl]-                                                         5%                                               2,3-dihydrobenzo[b]thiophene-7-sulfonamide, 1,1-                               dioxide, sodium salt                                                           water                        95%                                               ______________________________________                                    

The salt is added directly to the water with stirring to produce the solution, which may then be packaged for use.

EXAMPLE 13 Emulsifiable Concentrate

    ______________________________________                                         N--[(4-bromo-6-methoxypyrimidin-2-yl)aminocarbonyl]-                                                        20%                                               2,3-dihydro-2-methylbenzo[b]thiophene-7-sulfonamide,                           1,1-dioxide                                                                    chlorobenzene                74%                                               sorbitan monostearate and polyoxyethylene                                                                    6%                                               condensates thereof                                                            ______________________________________                                    

The ingredients are combined and stirred to produce a solution which can be emulsified in water for application.

Utility

Test results indicate that the compounds of the present invention are highly active preemergent or postemergent herbicides or plant growth regulants. Some of the compounds have particular utility for selective weed control in crops such as soybeans, wheat, barley and cotton. In particular, there is good selective weed control in soybeans.

The rates of application for the compounds of the invention are determined by a number of factors, including their use as plant growth modifiers or as herbicides, the crop species involved, the types of weeds to be controlled, weather and climate, formulations selected, mode of application, amount of foliage present, etc. In general terms, the subject compounds should be applied at levels of around 0.01 to 10 kg/ha, the lower rates being suggested for use on lighter soils and/or those having a low organic matter content, for plant growth modifiers or for situations where only short-term persistence is required.

The compounds of the invention may be used in combination with any other commercial herbicide; examples of which are those of the triazine, triazole, uracil, urea, amide, diphenylether, carbamate and bipyridylium types.

The herbicidal properties of the subject compounds were discovered in a number of greenhouse tests. The test procedures and results follow.

TEST A

Seeds of crabgrass (Digitaria spp.), barnyardgrass (Echinochloa crusgalli), wild oats (Avena fatua), sicklepod (Cassia obtusifolia), morningglory (Ipomoea spp.), cocklebur (Xanthium pensylvanicum), sorghum, corn, soybean, cotton, sugar beet, rice, wheat, cotton and purple nutsedge (Cyperus rotundus) tubers were planted and treated preemergence with the test chemicals dissolved in a non-phytotoxic solvent. At the same time, these crop and weed species were treated with a soil/foliage application. At the time of treatment, the plants ranged in height from 2 to 18 cm. Treated plants and controls were maintained in a greenhouse for sixteen days, after which all species were compared to controls and visually rated for response to treatment. The ratings, summarized in Table A, are based on a numerical scale extending from 0=no injury, to 10=complete kill. The accompanying descriptive symbols have the following meanings:

B=burn;

C=chlorosis/necrosis;

D=defoliation;

E=emergence inhibition;

G=growth retardation;

H=formative effects;

S=albinism;

U=unusual pigmentation;

X=axillary stimulation; and

6Y=abscised buds or flowers.

The ratings for the compounds tested by this procedure are presented in Table A. It will be seen that, at the low rates of application selected for this test, the compounds tested have utility for plant growth modification and also are highly active herbicides. ##STR17##

                  TABLE A                                                          ______________________________________                                                           Cmpd. 1    Cmpd. 2                                           Rate kg/ha        0.05       0.05                                              ______________________________________                                         POSTEMERGENCE                                                                  Morningglory      3C,6G      5C,9G                                             Cocklebur         10C        6C,9G                                             Sicklepod         1C,2H      3C,7G                                             Nutsedge          3C,8G      2C,8G                                             Crabgrass         4C,8G      6C,9G                                             Barnyardgrass     10C        10C                                               Wild Oats         0          0                                                 Wheat             0          2G                                                Corn              10C        3C,9G                                             Soybean           2H,3G      5G                                                Rice              5C,9G      5C,9G                                             Sorghum           10C        9C                                                Sugar beet        9C         5C,9G                                             Cotton            4C,9G      2C,9G                                             PREEMERGENCE                                                                   Morningglory      9G         8G                                                Cocklebur         8G         9H                                                Sicklepod         2C,7G      9G                                                Nutsedge          10E        9G                                                Crabgrass         2G         2C,8G                                             Barnyardgrass     4C,8H      3C,9H                                             Wild Oats         1C         1C                                                Wheat             2G         2G                                                Corn              2C,8G      10E                                               Soybean           1C,3G      1H                                                Rice              10E        10E                                               Sorghum           3C,9G      3C,9H                                             Sugar beet        10E        9G                                                Cotton            9G         8G                                                ______________________________________                                    

TEST B Postemergence

Two round pans (25 cm diameter by 12.5 cm deep) were filled with Woodstown sandy loam soil. One pan was planted with blackgrass (Alopecurus myosuroides), sugar beets, nutsedge (Cyperus rotundus) tubers, crabgrass (Digitaria sanquinalis), sicklepod (Cassia obtusifolia), teaweed (Sida spinosa), jimsonweed (Datura stramonium), velvetleaf (Abutilon theophrasti), and giant foxtail (Setaria faberii). The other pan was planted with wheat, cotton, rice, corn, soybean, wild oats (Avena fatua), cocklebur (Xantium pensylvanicum), morningglory (Ipomoea hederacea), johnsongrass (Sorghum halepense) and barnyardgrass (Echinochloa crusgralli). The plants were grown for approximately fourteen days, then sprayed postemergence with the chemicals dissolved in a non-phytotoxic solvent.

Preemergence

Two round pans (25 cm diameter by 12.5 cm deep) were filled with Woodstown sandy loam soil. One pan was planted with blackgrass, sugar beets, nutsedge, crabgrass, sicklepod, teaweed, jimsonweed, velvetleaf, and giant foxtail. The other pan was planted with wheat, cotton, rice, corn, soybeans, wild oats, cocklebur, morningglory, johnsongrass, and barnyardgrass. The two pans were sprayed preemergence with the chemicals dissolved in a non-phytotoxic solvent.

Treated plants and controls were maintained in the greenhouse for 28 days, then all treated plants were compared to controls and visually rated for plant response.

Response ratings are based on a scale of 0 to 10: where 0=no effect, and 10=complete control. The type of response is indicated by letters explained under Test A. A dash (-) response means no test.

Response ratings are contained in Table B.

                  TABLE B                                                          ______________________________________                                                   Compound 1  Compound 2                                               Rate g/ha   62     16     4   1   62   16   4    1                             ______________________________________                                         POSTEMERGENCE                                                                  Corn        10U    10U    9G  7G  10G  10G  9G   7G                            Wheat       0      0      0   0   0    0    0    0                             Rice        10C    9G     6G  4G  10G  10G  9G   7G                            Soybean     6G     4G     3G  2G  3G   1G   0    0                             Cotton      10C    8G     4G  2G  9G   6G   3G   0                             Sugar beet  10C    10G    9G  9G  10G  7G   2G   0                             Crabgrass   10G    9G     5G  2G  10G  10G  8G   3G                            Johnsongrass                                                                               10C    9G     7G  3G  10G  9G   9G   6G                            Blackgrass  9C     8G     2G  0   10G  9G   6G   2G                            Barnyardgrass                                                                              10C    9G     5G  2G  10G  10G  7G   4G                            Nutsedge    4G     2G     0   0   0    0    0    0                             Giant Foxtail                                                                              9G     6G     4G  0   10G  9G   7G   4G                            Wild Oats   0      0      0   0   0    0    0    0                             Cocklebur   8G     6G     3G  0   10G  6G   2G   0                             Morningglory                                                                               9G     8G     6G  2G  10G  6G   2G   0                             Teaweed     10G    7G     5G  2G  8G   4G   0    0                             Sicklepod   7G     4G     4G  0   4G   2G   0    0                             Jimsonweed  10G    5G     3G  2G  10G  7G   2G   0                             Velvetleaf  10C    6G     6G  4G  10G  6G   3G   0                             ______________________________________                                         Rate g/ha   250    62     16  4   250  62   16   4                             ______________________________________                                         PREEMERGENCE                                                                   Corn        10G    7G     3G  0   10G  9G   4G   0                             Wheat       0      0      0   0   8G   2G   0    0                             Rice        10G    10G    8G  4G  10G  10G  10G  8G                            Soybean     5G     2G     0   0   6G   1G   0    0                             Cotton      8G     3G     0   0   9G   7G   2G   0                             Sugar beet  8G     6G     2G  0   10G  9G   3G   0                             Crabgrass   10G    9G     3G  0   10G  9G   8G   3G                            Johnsongrass                                                                               10G    10G    8G  3G  10G  10G  9G   8G                            Blackgrass  10G    10G    8G  3G  10G  10G  8G   7G                            Barnyardgrass                                                                              10G    10G    7G  2G  10G  9G   9G   5G                            Nutsedge    10G    9G     3G  0   10G  9G   7G   3G                            Giant Foxtail                                                                              --     --     --  --  --   --   --   --                            Wild Oats   2G     0      0   0   4G   0    0    0                             Cocklebur   7G     3G     0   0   6G   2G   0    0                             Morningglory                                                                               9G     6G     3G  0   8G   3G   0    0                             Teaweed     9G     8G     4G  0   10G  9G   8G   2G                            Sicklepod   10G    8G     4G  0   9G   7G   4G   0                             Jimsonweed  10G    10G    8G  3G  10G  9G   7G   2G                            Velvetleaf  9G     8G     3G  0   10G  8G   5G   2G                            ______________________________________                                    

TEST C

Three 25-cm diameter plastic pots were filled with a light soil. One pan was planted to short rows of corn, soybeans, and cotton, planting depth 2.5 cm. The other two pots were planted to the following weed species, 8 or 9 species per pot: crabgrass (Digitaria sp.), johnsongrass, (Sorghum halepense), barnyardgrass (Echinochloa crusgalli), nutsedge (Cyperus rotundus), giant foxtail (Setaria faberii), green foxtail (Setaria viridis), cocklebur (Xanthium pensylvanicum), morningglory (Ipomoea hederacea), teaweed (Sida spinosa), sicklepod (Cassia obtusifolia), jimsonweed (Datura stramonium), velvetleaf (Abutilon theophrasti), bindweed (Convolvulus arvensis), coffeeweed (Sesbania exaltata), lambsquarters (Chenopodium album), pigweed (Amaranthus retroflexus),and purslane (Portulaca oleracea). All of the foregoing weed species were planted at a depth of 0.5 to 1.0 cm, except for cocklebur and nutsedge which were planted at a depth of 2.5 cm. The plantings were treated preemergence with the test chemicals dissolved in a non-phytotoxic solvent. At the same time, the same crops and weed species, from plantings made 10 to 21 days previously, were treated with a soil/foliage application. Treated plants and controls were maintained in a greenhouse for 3 to 4 weeks after which all species were compared to controls and visually rated for response to treatment with 0 indicating no injury and 100 indicating that the plants were dead. The data are summarized in Table C.

                                      TABLE C                                      __________________________________________________________________________     Compound 1                     Compound 2                                      Rate gm/ha 250                                                                               125                                                                               62 31 16 8  4 250                                                                               125                                                                               62 31 16 8 4                              __________________________________________________________________________     POSTEMERGENCE                                                                  Corn       100                                                                               100                                                                               100                                                                               100                                                                               90 85 80                                                                               100                                                                               100                                                                               100                                                                               100                                                                               90 85                                                                               75                             Cotton     -- -- -- -- -- -- --                                                                               -- -- -- -- -- --                                                                               --                             Soybean    55 40 35 30 25 20 20                                                                               45 40 30 25 20 15                                                                               0                              Crabgrass  100                                                                               100                                                                               95 85 75 65 40                                                                               100                                                                               95 95 85 75 50                                                                               35                             Johnsongrass                                                                              100                                                                               100                                                                               100                                                                               100                                                                               100                                                                               100                                                                               80                                                                               100                                                                               100                                                                               100                                                                               100                                                                               100                                                                               95                                                                               85                             Barnyardgrass                                                                             100                                                                               100                                                                               100                                                                               95 80 75 50                                                                               100                                                                               100                                                                               100                                                                               90 85 80                                                                               65                             Nutsedge   100                                                                               95 80 75 55 35 30                                                                               95 85 80 75 50 20                                                                               0                              Giant foxtail                                                                             100                                                                               100                                                                               100                                                                               95 85 80 70                                                                               100                                                                               100                                                                               95 90 85 80                                                                               70                             Green foxtail                                                                             100                                                                               100                                                                               100                                                                               95 85 85 70                                                                               100                                                                               100                                                                               100                                                                               90 90 85                                                                               70                             Cocklebur  -- 100                                                                               100                                                                               85 85 65 40                                                                               100                                                                               90 85 70 65 40                                                                               20                             Morningglory                                                                              -- 95 90 80 75 55 35                                                                               95 85 80 70 70 50                                                                               30                             Teaweed    -- 90 85 80 80 60 40                                                                               100                                                                               90 90 65 60 50                                                                               35                             Sicklepod  -- 90 85 80 65 50 40                                                                               100                                                                               95 85 70 55 25                                                                               15                             Jimsonweed -- 85 80 85 75 50 40                                                                               100                                                                               90 80 50 40 20                                                                               15                             Velvetleaf 95 90 85 80 65 40 30                                                                               95 85 75 75 55 25                                                                               20                             Bindweed   85 60 40 35 25 15 0 70 60 60 45 40 25                                                                               15                             Coffeeweed 100                                                                               100                                                                               100                                                                               85 80 65 45                                                                               100                                                                               100                                                                               90 65 60 35                                                                               25                             Lambsquarter                                                                              100                                                                               95 90 90 70 60 35                                                                               100                                                                               100                                                                               95 90 80 40                                                                               15                             Pigweed    100                                                                               100                                                                               100                                                                               100                                                                               85 75 40                                                                               100                                                                               100                                                                               100                                                                               100                                                                               95 80                                                                               45                             Purslane   100                                                                               100                                                                               95 85 75 65 50                                                                               100                                                                               100                                                                               100                                                                               85 85 40                                                                               35                             PREEMERGENCE                                                                   Corn       100                                                                               100                                                                               95 85 75 45 20                                                                               100                                                                               100                                                                               95 80 60 20                                                                               0                              Cotton     100                                                                               100                                                                               85 75 35 15 0 100                                                                               90 70 25 15 0 0                              Soybean    75 40 25 0  0  0  0 50 35 20 0  0  0 0                              Crabgrass  100                                                                               100                                                                               100                                                                               100                                                                               85 60 20                                                                               100                                                                               100                                                                               100                                                                               100                                                                               85 75                                                                               55                             Johnsongrass                                                                              100                                                                               100                                                                               100                                                                               100                                                                               100                                                                               95 75                                                                               100                                                                               100                                                                               100                                                                               100                                                                               100                                                                               90                                                                               85                             Barnyardgrass                                                                             100                                                                               100                                                                               100                                                                               100                                                                               95 85 35                                                                               100                                                                               100                                                                               100                                                                               100                                                                               90 85                                                                               55                             Nutsedge   100                                                                               100                                                                               100                                                                               100                                                                               95 85 45                                                                               100                                                                               100                                                                               100                                                                               95 75 45                                                                               25                             Giant foxtail                                                                             100                                                                               100                                                                               100                                                                               95 90 30 0 100                                                                               100                                                                               100                                                                               90 85 80                                                                               20                             Green foxtail                                                                             100                                                                               100                                                                               95 95 80 15 0 100                                                                               100                                                                               100                                                                               90 90 55                                                                               15                             Cocklebur  100                                                                               100                                                                               85 55 35 25 0 -- -- -- -- -- --                                                                               --                             Morningglory                                                                              100                                                                               100                                                                               95 90 85 35 0 100                                                                               100                                                                               100                                                                               85 60 20                                                                               0                              Teaweed    100                                                                               100                                                                               100                                                                               85 75 45 15                                                                               100                                                                               100                                                                               95 85 55 25                                                                               15                             Sicklepod  100                                                                               100                                                                               95 85 65 45 15                                                                               100                                                                               90 90 75 40 20                                                                               15                             Jimsonweed 100                                                                               100                                                                               100                                                                               95 90 60 20                                                                               100                                                                               100                                                                               100                                                                               100                                                                               100                                                                               90                                                                               75                             Velvetleaf 100                                                                               100                                                                               95 95 80 65 15                                                                               100                                                                               95 90 80 50 25                                                                               15                             Bindweed   100                                                                               100                                                                               90 85 75 55 25                                                                               100                                                                               95 90 85 80 60                                                                               45                             Coffeeweed 100                                                                               100                                                                               85 80 60 35 15                                                                               100                                                                               90 90 80 45 30                                                                               20                             Lambsquarter                                                                              100                                                                               100                                                                               100                                                                               100                                                                               90 75 50                                                                               100                                                                               100                                                                               100                                                                               100                                                                               90 80                                                                               75                             Pigweed    100                                                                               100                                                                               100                                                                               100                                                                               90 75 50                                                                               100                                                                               100                                                                               100                                                                               100                                                                               90 80                                                                               75                             Purslane   100                                                                               100                                                                               100                                                                               100                                                                               100                                                                               80 50                                                                               100                                                                               100                                                                               100                                                                               100                                                                               100                                                                               85                                                                               80                             __________________________________________________________________________

TEST D

Two plastic pans lined with polyethylene liners were filled with prepared Woodstown sandy loam soil. One pan was planted with seeds of wheat (Triticum aestivum), barley (Hordeum vulgare), wild oats (Avena fatua), cheatgrass (Bromus secalinus), blackgrass (Alopecurus myosuroides), annual bluegrass (Poa annua), green foxtail (Setaria viridis), Italian ryegrass (Lolium multiflorum) and rapeseed (Brassica napus). The other pan was planted with seeds of Russian thistle (Salsola kali), cleavers (Galium aparine), speedwell (Veronica persica), kochia (Kochia scoparia), shepherdspurse (Capsella bursa-pastoris), Matricaria inodora, black nightshade (Solanum nigrum), wild buckwheat (Polygonum convolvulus) and sugar beets (Beta vulgaris). The above two pans were treated preemergence. At the same time two pans in which the above plant species were already growing were treated postemergence. Plant height at the time of treatment ranged from 1-20 cm depending on plant species.

The compounds applied were diluted with a nonphytotoxic solvent and sprayed over-the-top of the pans. An untreated control and a solvent alone control were included for comparison. All treatments were maintained in the greenhouse for 19-22 days at which time the treatments were compared to the controls and the effects visually rated utilizing the same rating system as described for Test A. The recorded data are presented in Table D.

                                      TABLE D                                      __________________________________________________________________________                 Compound 1               Compound 2                                Rate kg/ha  .125                                                                              .06                                                                               .03                                                                               .015                                                                              .008                                                                              .004                                                                              .002                                                                              .0001                                                                               .125                                                                              .06                                                                               .03                                                                               .015                                                                              .008                                                                              .004                                                                              .002                                                                              .0001               __________________________________________________________________________     POSTEMERGENCE                                                                  wheat       2G 0  0  0  0  0  0  0    0  0  0  0  0  0  0  0                   barley      8G 5G 4G 3G 2G 0  0  0    6G 5G 4G 4G 5G 2G 2G 0                   wild oats   0  0  0  0  0  0  0  0    0  0  0  0  0  0  0  0                   cheatgrass  6G 5G 3G 0  0  0  0  0    6G 4G 4G 2G 0  0  0  0                   blackgrass  10C                                                                               9G 7G 5G 3G 0  0  --   9G 9G 8G 5G 3G 0  0  --                  annual bluegrass                                                                           10C                                                                               9G 9G 4G 4G 0  0  --   10C                                                                               9G 8G 5G 2G 2G 0  --                  green foxtail                                                                              10C                                                                               10C                                                                               10C                                                                               10C                                                                               8G 6G 4G --   10C                                                                               10C                                                                               10C                                                                               10C                                                                               8G 7G 5G --                  Italian ryegrass                                                                           10C                                                                               8G 8G 5G 3G 2G 2G --   9G 6G 5G 3G 2G 0  0  --                  rapeseed    10C                                                                               10C                                                                               10C                                                                               10C                                                                               10C                                                                               9G 7G --   10C                                                                               10C                                                                               10C                                                                               10C                                                                               9G 8G 5G --                  Matricaria inodora                                                                         -- -- -- -- -- -- -- --   -- -- -- -- -- -- -- --                  Galium aparine                                                                             -- -- -- -- -- -- -- --   -- -- -- -- -- -- -- --                  Russian thistle                                                                            -- -- -- -- -- -- -- --   -- -- -- -- -- -- -- --                  shepherdspurse                                                                             -- -- -- -- -- -- -- --   -- -- -- -- -- -- -- --                  kochia      -- -- -- -- -- -- -- --   -- -- -- -- -- -- -- --                  black nightshade                                                                           -- -- -- -- -- -- -- --   -- -- -- -- -- -- -- --                  speedwell   10C                                                                               10C                                                                               10C                                                                               3G 0  0  0  0    7G 0  0  0  0  0  0  0                   wild buckwheat                                                                             10C                                                                               5G 2G 0  -- 2G 2G 0    7G 2G 2G -- 0  0  0  0                   sugar beets 10C                                                                               9G 9G 4G 5G 3G 3G 3G   10C                                                                               10C                                                                               10C                                                                               4G 3G 3G 0  0                   PREEMERGENCE                                                                   wheat       0  0  0  0  0  0  0  0    0  0  0  0  0  0  0  0                   barley      6G 0  2G 0  0  0  0  0    8G 7G 7G 7G 3G 3G 0  0                   wild oats   0  0  0  0  0  0  0  0    0  0  0  0  0  0  0  0                   cheatgrass  5G 2G 0  0  0  0  0  0    7G 3G 0  0  0  0  0  0                   blackgrass  8G 8G 8G 8G 7G 3G 2G 0    9G 8G 8G 7G 6G 4G 2G 1G                  annual bluegrass                                                                           9G 9G 9G 8G 8G 7G 5G 3G   9G 9G 9G 8G 5G 5G 3G 2G                  green foxtail                                                                              9G 8G 5G 2G 0  0  0  0    9G 7G 7G 6G 4G 2G 0  0                   Italian ryegrass                                                                           8G 8G 7G 4G 4G 3G 3G 0    8G 7G 6G 5G 4G 2G 2G 2G                  rapeseed    9G 9G 9G 8G 7G 4G 4G 2G   9G 9G 9G 7G 5G 2G 2G 2G                  Matricaria inodora                                                                         9G 9G 8G 8G 8G 6G 6G 5G   8G 7G 7G 7G 6G 5G 4G 3G                  Galium aparine                                                                             10C                                                                               9G 9G 5G 5G 4G 4G 0    9G 8G 9G 6G 5G 0  0  0                   Russian thistle                                                                            8G 8G 3G 2G 2G 2G 0  0    6G 6G 3G 0  0  0  0  0                   shepherdspurse                                                                             10C                                                                               10C                                                                               9G 9G 9G 7G 6G 0    10C                                                                               10C                                                                               9G 9G 8G 6G 5G 3G                  kochia      10C                                                                               10C                                                                               10C                                                                               10C                                                                               8G 8G 4G 4G   10C                                                                               10C                                                                               10C                                                                               9G 7G 6G 6G 3G                  black nightshade                                                                           9G 9G 9G 8G 8G 6G 3G 0    9G 9G 9G 8G 8G 8G 6G 4G                  speedwell   10C                                                                               10C                                                                               10C                                                                               10C                                                                               9G 7G 5G 0    9G 6G 3G 0  0  0  0  0                   wild buckwheat                                                                             8G 8G 7G 2G 0  0  0  0    8G 5G -- 0  0  0  0  0                   sugar beets 10C                                                                               10C                                                                               10C                                                                               10C                                                                               8G 8G 6G 6G   9G 9G 9G 9G 7G 8G 5G 5G                  __________________________________________________________________________ 

What is claimed is:
 1. The compound N-[(4-bromo-6-methoxypyrimidin-2-yl)aminocarbonyl]-2,3-dihydrobenzo[b]thiophene-7-sulfonamide, 1,1-dioxide.
 2. The compound N-[(4-bromo-6-methoxypyrimidin-2-yl)aminocarbonyl]-2,3-dihydro-2-methylbenzo[b]thiophene-7-sulfonamide, 1,1-dioxide.
 3. A composition suitable for controlling the growth of undesired vegetation which comprises an effective amount of the compound of claim 1 and at least one of the following: surfactant, solid or liquid diluent.
 4. A composition suitable for controlling the growth of undesired vegetation which comprises an effective amount of the compound of claim 2 and at least one of the following: surfactant, solid or liquid diluent.
 5. A method for controlling the growth of undesired vegetation which comprises applying to the locus to be protected an effective amount of the compound of claim
 1. 6. A method for controlling the growth of undesired vegetation which comprises applying to the locus to be protected an effective amount of the compound of claim
 2. 